CN110004477A - A kind of electrolyte and the method for preparing Mg alloy surface black film layer with the electrolyte - Google Patents
A kind of electrolyte and the method for preparing Mg alloy surface black film layer with the electrolyte Download PDFInfo
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- CN110004477A CN110004477A CN201910312198.XA CN201910312198A CN110004477A CN 110004477 A CN110004477 A CN 110004477A CN 201910312198 A CN201910312198 A CN 201910312198A CN 110004477 A CN110004477 A CN 110004477A
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- Prior art keywords
- electrolyte
- film layer
- magnesium alloy
- fluoride
- black film
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Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 80
- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002679 ablation Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000004140 cleaning Methods 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 230000002000 scavenging effect Effects 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- HLJCWGPUCQTHFY-UHFFFAOYSA-H disodium;hexafluorotitanium(2-) Chemical compound [F-].[F-].[Na+].[Na+].F[Ti](F)(F)F HLJCWGPUCQTHFY-UHFFFAOYSA-H 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 229960002050 hydrofluoric acid Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- -1 salt compound Chemical class 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
Abstract
The invention discloses a kind of electrolyte and the methods for preparing Mg alloy surface black film layer with the electrolyte.Electrolyte composition is as follows: 8~15g/L hydroxide, 10~15g/L fluoride, 20~30g/L phosphate, 4~14g/L ferrate, 1~5g/L fluotitanate, 10~20g/L Organic Alcohol, 80~300g/L ablation inhibitor, solvent is deionized water.Higher blackness value can be realized on compared with film layer, effectively avoid the problem that scrapping what processing complex precise product occurred often because of Partial ablation.
Description
Technical field
The invention belongs to magnesium alloy processing method technical field, it is related to a kind of electrolyte and prepares magnesium alloy with the electrolyte
The method of surface black film layer.
Background technique
There is magnesium alloy low-density, Gao Biqiang/rigidity, high-damping, good thermal conductivity and electromagnetic wave shielding and magnesium to close
Golden product is easily recycled a series of advantage of uniquenesses such as no pollution to the environment, is referred to as " 21 century green work by people
Journey material " is widely used in fields such as space flight and aviation, defence and military, automobile, 3C Products.
Magnesium alloy differential arc oxidation technology is interacted between magnesium alloy substrate and solution under electric field action, thus in matrix
Surface in situ grows the novel surface processing technique of the ceramic film based on magnesia, and gained ceramic film has good
Wear-and corrosion-resistant feature.
Magnesium alloy differential arc oxidation black film layer on the one hand in terms of dicoration because its embodied it is sedate, serious due to deep disappeared
The person's of expense favor；Another aspect black film layer such as extinction, heat absorption, heat radiation unique advantage in terms of functionality make it in electronics and
Optical field also has broad application prospects.
Currently, the country is existing largely to prepare the patent of black micro-arc oxidation ceramic layer in Mg alloy surface.Such as Chinese patent
" magnesium alloy differential arc oxidation electrolyte and the technique that Mg alloy surface black ceramicization is handled using the electrolyte " (application number
201310439874.2), Chinese patent " a kind for the treatment of method of black hard microarc oxidation ceramic membrane on surface of magnesium alloy " " (application
Number 201010530357.2), what above-mentioned patent coloured that salt is all made of because of it is mantoquita, and there are mantoquitas in cathode when mass production
Upper precipitation causes coloring ion in solution to reduce to cause the stability of solution poor, and the consistency of gained film layer is poor." magnesium
Alloy differential arc oxidation prepares the electrolyte and method of black ceramic film layer " (application number 201510510427.0), a kind of " magnesium alloy
Surface by micro-arc oxidation prepares the black ceramic membrane layer process of high absorptance " (application number 201310649416.1), " magnesium alloy differential arc
Aoxidizing low energy consumption black ceramic membrane and preparation method " patents, the coloring salt such as (application number 201210476200.5) is all made of
It is vanadic salts, vanadic salts has heavy metal pollution.In addition, magnesium alloy gold is active, there is inflammable attribute, existed using the prior art
Easily there is Partial ablation in such as threaded hole, blind chamber and edge when the product of processing structure complex precise so as to cause production
The problem of product are scrapped.
Summary of the invention
The object of the present invention is to provide a kind of electrolyte, can carry out differential arc oxidation to complicated magnesium alloy.
The technical scheme adopted by the invention is that a kind of electrolyte, electrolyte composition is as follows:
8~15g/L hydroxide, 10~15g/L fluoride, 20~30g/L phosphate, 4~14g/L ferrate, 1~
5g/L fluotitanate, 10~20g/L Organic Alcohol, 80~300g/L ablation inhibitor, solvent is deionized water.
The features of the present invention also characterized in that
Electrolyte solute composition is as follows:
10~12g/L hydroxide, 12~14g/L fluoride, 22~25g/L phosphate, 4~14g/L ferrate, 1
~5g/L fluotitanate, 15~18g/L Organic Alcohol, 150~200g/L ablation inhibitor, solvent is deionized water.
Hydroxide is sodium hydroxide or potassium hydroxide；Ferrate is one of potassium ferrate, Na2Fe04 or two
The mixture of kind；Fluotitanate is the mixture of one or both of potassium fluotitanate, titanium sodium fluoride；Fluoride be potassium fluoride,
One of sodium fluoride, hydrogen fluoride ammonia and ammonium fluoride or a variety of mixtures；Phosphate be sodium dihydrogen phosphate, disodium hydrogen phosphate,
One of tertiary sodium phosphate, calgon, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or a variety of mixtures；Organic Alcohol is second two
One of alcohol, glycerine, isopropanol or a variety of mixtures；Ablation inhibitor is hexa, own subunit diamines, ammonia
One of three ethyl alcohol of base or a variety of mixtures.
It, can be it is a further object to provide a kind of method for preparing Mg alloy surface black film layer with electrolyte
Mg alloy surface forms the black film layer of high blackness value.
Another technical solution of the present invention is a kind of side that Mg alloy surface black film layer is prepared with electrolyte
Method, specifically includes the following steps:
Step 1 prepares electrolyte, for use；
Electrolyte is the electrolyte of claim 1-3 any one；
Magnesium alloy is first immersed in acid pretreatment liquid and cleans 2~10min, then washed by step 2；
Magnesium alloy after step 2 cleaning is first immersed in alkali cleaning pretreatment liquid and is cleaned, then washed by step 3；
Magnesium alloy after step 3 cleaning is placed in electrolyte and carries out micro-arc oxidation treatment by step 4, magnesium alloy table
Face forms black film layer；
Step 5, to through step 4, treated that magnesium alloy cleaned, is dried.
Acid pretreatment liquid in step 2 is mixed solution A or mixed solution B, and mixed solution A is hydrofluoric acid, sulfuric acid
Mixed solution, the volume fraction of hydrofluoric acid are 15%~20%, and the volume fraction of sulfuric acid is 5%~8%；Mixed solution B is hydrogen
The mixed solution of fluoric acid and nitric acid, the volume fraction of hydrofluoric acid are 5%~10%, and the volume fraction of nitric acid is 5%~10%.
Alkali cleaning pretreatment liquid in step 3 are as follows: concentration is the mixed of 20~40g/L tertiary sodium phosphate and 20~40g/L sodium carbonate
Liquid is closed, cleaning temperature is 70~95 DEG C, and scavenging period is 2~10min.
Alkali cleaning pretreatment liquid in step 3 are as follows: concentration is the mixed of 20~40g/L sodium carbonate and 10~20g/L sodium hydroxide
Liquid is closed, cleaning temperature is 70~95 DEG C, and scavenging period is 2~10min.
Alkali cleaning pretreatment liquid in step 3 are as follows: concentration is 40~60g/L sodium hydroxide, and cleaning temperature is 50~70 DEG C, clearly
Washing the time is 1~5min.
Step 4 electrical parameters in micro-arc oxidation process are as follows: frequency is 400~800Hz, and duty ratio is 5~30%, positive negative pulse stuffing number
Than 1:0~10:1, the differential arc oxidation time is 5~60min, and powered-on mode is constant current mode or constant voltage mode；
When powered-on mode is constant current mode, current density is 0.5~60A/dm2；When powered-on mode is constant voltage mode, voltage
For 300~580V.
The detailed process of step 5 are as follows: by treated that magnesium alloy is placed in 60~95 DEG C of pure water cleans 0.5 through step 4
Then~5min puts it into the baking oven that temperature is 80~110 DEG C and dries, drying time is 8~30min.
The beneficial effects of the present invention are:
Electrolyte of the invention, using ferrate as main colorant, fluotitanate is avoided that all as auxiliary colorant
As copper coloring salt in oxidation process the continuous precipitating metal copper of cathode and cause to colour salinity loss too fast and vanadium coloring salt
The intractable problem of solution；High blackness value can be realized in electrolyte of the invention on compared with film layer；It is added in the present invention few
The solution stabilizer of amount can effectively extend the service life of solution, reduce the use cost of solution；In electrolyte of the invention
By the way that the ablation inhibitor of appropriate concentration is added, it can effectively change the interface state of solution and product surface, change oxidation process
In flash-over characteristic, and then effectively avoid the problem that in being scrapped because of Partial ablation of occurring often of processing complex precise product.
The method that the present invention prepares Mg alloy surface black film layer with electrolyte, prepared black film layer thickness (5~
10 μm) it is low when can reach higher blackness value (L value is smaller than 27) and hemispherical emissivity (ε is greater than 0.85), meeting blackness
The processing cost of film layer is effectively reduced while performance requirement；The present invention prepares the side of Mg alloy surface black film layer with electrolyte
Method, it is wider to the apparatus adaptability of differential arc oxidation, can be prepared using dual-pulse power supply or pulse power supply have excellent performance it is black
Color film layer.
Detailed description of the invention
Fig. 1 is a kind of macro morphology for the embodiment of the method 1 that Mg alloy surface black film layer is prepared with electrolyte of the present invention
Figure；
Fig. 2 is a kind of macro morphology for the embodiment of the method 2 that Mg alloy surface black film layer is prepared with electrolyte of the present invention
Figure；
Fig. 3 is a kind of microscopic appearance for the embodiment of the method 3 that Mg alloy surface black film layer is prepared with electrolyte of the present invention
Figure.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of electrolyte, electrolyte composition are as follows:
Main film forming agent are as follows: 8~15g/L hydroxide, 10-15g/L fluoride, 20~30g/L phosphate；Colorant are as follows:
4-14g/L ferrate, 1~5g/L fluotitanate；Solution stabilizer are as follows: 10~20g/L Organic Alcohol；Ablation inhibitor: 80~
300g/L, solvent are deionized water.
Preferably, hydroxide is sodium hydroxide or potassium hydroxide；Ferrate is potassium ferrate, one in Na2Fe04
Kind or two kinds of mixture；Fluotitanate is the mixture of one or both of potassium fluotitanate or titanium sodium fluoride；Fluoride is
One or more of potassium fluoride, sodium fluoride, hydrogen fluoride ammonia and ammonium fluoride；Phosphate is sodium dihydrogen phosphate, disodium hydrogen phosphate, phosphorus
One or more of sour trisodium, calgon, ammonium dihydrogen phosphate, diammonium hydrogen phosphate；Organic Alcohol are as follows: ethylene glycol, glycerine,
One or more of isopropanol；Ablation inhibitor be one of hexa, own subunit diamines, Triaethanolamine or
It is several.
Differential arc oxidation coloring principle is directly to participate in reaction in oxidation process by the metal salt in electrolyte, generate
The color of contained metal salt compound is exactly the color of ceramic layer.Therefore for differential arc oxidation coloring, most critical is reaction
The color that compound contained by the film layer obtained afterwards is presented, the color of these compounds determine the color of film layer.Theoretically, molysite
Compound in, have ferrous oxide and ferroso-ferric oxide be atrament, then found in verification experimental verification, basis be electrolysed
Molysite (such as ferric sulfate, ironic citrate, ferric citrate) is added in liquid, because iron ion is inhaled under electric field action in oxidation process
It is attached to metal surface and easily preferentially forms iron oxide, lead to not also be only possible to produce grey film after forming effective film layer or film forming
Layer.It, can be with by using two kinds of coloring salt of ferrate and fluotitanate as colorant in electrolyte system of the invention
Effectively black film layer is prepared in Mg alloy surface.Test discovery, when ferrate concentration is lower than 4g/L, surface is difficult to be formed black
Color film layer；For colorant ferrate when concentration is higher than 14g/L, easily there is ablation phenomen in film layer edge；Colorant fluotitanate
When concentration is lower than 1g/L, film layer grey or brown；When fluotitanate concentration is higher than 5g/L, film layer is coarse and face easily occurs in surface
The non-uniform phenomenon of color.
Compared with prior art, well, addition Organic Alcohol can effectively extend the solution system to the stabilization in electrolyte of the present invention
Service life, reduce solution maintenance cost；Ablation inhibitor is added, solution and magnesium alloy table on the one hand can be effectively changed
Interface state between face, make ablation inhibitor chemisorption in Mg alloy surface to form more stable absorption on surface
Film, the adsorbed film have biggish shielding action to Mg alloy surface, slow down the reaction rate of magnesium and oxygen, are stabilized oxidation film
Slowly growth, to make film layer more dense uniform；The resistance of another aspect organic additive is larger, can reduce the electricity of solution
Conductance, so reduce solution in solute ions migration rate, realize in oxidation process in solution solute ions sublevel ladder into
Enter in film layer, and then avoids in portions such as blind chamber, the threaded holes for handling surface quality poor die casting and product structure complexity
There is the problem of ablation leads to scrap of the product in position.
A method of Mg alloy surface black film layer being prepared with electrolyte, specifically includes the following steps:
Step 1 prepares electrolyte, and 9~14g/L hydroxide, 2~20g/L ferric acid are sequentially added into deionized water
Salt, 1~5g/L fluotitanate, 9~15g/L fluoride, 21~55g/L phosphate, 10~20g/L Organic Alcohol, 30~500g/L
30~60min is sufficiently stirred, for use in prepared electrolyte by ablation inhibitor at room temperature.
Magnesium alloy is first immersed in acid pretreatment liquid and is cleaned, then washed by step 2；
Acid pretreatment liquid is the mixed solution of hydrofluoric acid and sulfuric acid, wherein the volume fraction of HF is 15%~20%,
H2SO4Volume fraction be 5%~8%；Or the mixed solution of hydrofluoric acid and nitric acid, wherein the volume fraction of HF be 5%~
10%, HNO3Volume fraction be 5%~10%, scavenging period be 2~10min.
Magnesium alloy after step 2 cleaning is first immersed in alkali cleaning pretreatment liquid and is cleaned, then washed by step 3；
Alkali cleaning pretreatment liquid are as follows: concentration is the mixed liquor of 20~40g/L tertiary sodium phosphate and 20~40g/L sodium carbonate, cleaning
Temperature is 70~95 DEG C, and scavenging period is 2~10min；
Alkali cleaning pretreatment liquid can be with are as follows: and concentration is the mixed liquor of 20~40g/L sodium carbonate and 10~20g/L sodium hydroxide,
Cleaning temperature is 70~95 DEG C, and scavenging period is 2~10min；
Alkali cleaning pretreatment liquid can be with are as follows: concentration is 40~60g/L sodium hydroxide, and cleaning temperature is 50~70 DEG C, cleaning
Time is 1~5min.
Magnesium alloy after step 3 cleaning is placed in electrolyte and carries out micro-arc oxidation treatment by step 4, magnesium alloy table
Face forms black film layer；Electrical parameters in micro-arc oxidation process are as follows: frequency is 400~800Hz, and duty ratio is 5~30%, positive negative pulse stuffing
For number than 1:0~10:1, the differential arc oxidation time is 5~60min, and powered-on mode is constant current mode or constant voltage mode；Powered-on mode is
When constant current mode, current density is 1~20A/dm2；When powered-on mode is constant voltage mode, voltage is 300~580V.
Step 5, by through step 4 treated magnesium alloy is placed in 60~95 DEG C of pure water 0.5~5min of cleaning, then will
It is put into the baking oven that temperature is 80~110 DEG C and dries, and drying time is 8~30min.
In the above manner, the method for the invention for preparing Mg alloy surface black film layer with electrolyte, obtained black
Film performance is excellent, and film layer L value minimum can test 96h, excellent (the hundred lattice test of membranous layer binding force up to 23 by neutral salt spray
Up to 4B or more), hemispherical emissivity reaches as high as 0.88, and the test of hundred lattice falls off without film layer after boiling test (boiling in 80 DEG C of water) 2h
Phenomenon；The micro-arc oxidation electrolyte of use is in alkalescent, and environmental pollution is small, harm to the human body is small；Preparation process is simple, solution
Component is few, and short preparation period, solution regulation are simple, high-efficient, at low cost, be applicable to the magnesium alloy of the different trades mark, it can be achieved that
Industrialized mass production.
Embodiment 1
Step 1 sequentially adds 10g/L sodium hydroxide, 5g/L potassium ferrate, 5g/L potassium fluotitanate, 9g/ into deionized water
L potassium fluoride, 30g/L calgon, 10g/L ethylene glycol, 150g/L hexa obtain electrolyte；Electrolyte is existed
30min is sufficiently stirred at room temperature, for use；
Step 2, by AZ91D magnesium alloy computor-keyboard (area 6dm2) it is placed in the HF that volume fraction is 15%, volume point
The H of number 5%2SO4Scavenging period 0.5min, is then washed in pickling pretreatment liquid；
Step 3, again will the AZ91D magnesium alloy computor-keyboard that handled by step 2 to be placed in concentration be 30g/L tertiary sodium phosphate,
In 30g/L sodium carbonate alkali cleaning pretreatment liquid, temperature control is 80 DEG C, then scavenging period 5min is washed；
The AZ91D magnesium alloy computor-keyboard handled by step 3 is placed in prepared electrolyte, magnesium alloy by step 4
Computor-keyboard connects equipment anode, and stainless steel carries out at differential arc oxidation magnesium alloy computor-keyboard after connecting with the mains as cathode
Reason.Differential arc oxidation electrical parameter are as follows: constant current mode, current density 2A/dm2, frequency 500Hz, duty ratio 12%, positive pulse
It is 1, negative pulse number is 0, and the differential arc oxidation time is 20min；
Step 5 will be placed in 80 DEG C of pure water after immersion 3min by the AZ91D magnesium alloy computor-keyboard that step 4 is handled,
It places into the baking oven that temperature is 110 DEG C and dries 8min.Gained film performance is as shown in table 1.Macro morphology as shown in Figure 1, from
In it can be seen that keyboard film layer colors black and uniformity, appearance is visible by naked eyes defect.
Embodiment 2
Step 1 sequentially adds 10g/L sodium hydroxide into deionized water, 10g/L Na2Fe04,1g/L potassium fluotitanate,
10g/L sodium fluoride, 20g/L ammonium dihydrogen phosphate, 20g/L isopropanol, 200g/L Triaethanolamine obtain electrolyte；By electrolyte
30min is sufficiently stirred at room temperature, for use；
Step 2, by AZ31D magnesium alloy computer shell (area 12dm2) it is put into 8% (volume fraction) HF, 6% (volume point
Number) HNO3Scavenging period 0.2min, is then washed in pickling pretreatment liquid；
The AZ31D magnesium alloy computer shell handled by step 2 is put into 60g/L sodium hydroxide, temperature control by step 3 again
60 DEG C are made as, then scavenging period 3min is washed；
The AZ31D magnesium alloy computer shell handled by step 3 is placed in prepared electrolyte, AZ31D magnesium by step 4
Alloy computer shell connects equipment anode, and stainless steel carries out differential arc oxidation to magnesium alloy computor-keyboard after connecting with the mains as cathode
Processing.Differential arc oxidation electrical parameter are as follows: constant current mode, current density 3A/dm2, frequency 500Hz, duty ratio 15%, positive arteries and veins
Punching is 1, negative pulse 1, and the differential arc oxidation time is 10min；
Step 5 will be placed in 90 DEG C of pure water after immersion 1min by the AZ31D magnesium alloy computer shell that step 4 is handled, then
It is put into the baking oven that temperature is 80 DEG C and dries 20min.Gained film performance is as shown in table 1.Macro morphology is as shown in Fig. 2, from figure
In as can be seen that prepared computer shell appearance in black and color it is uniform.
Embodiment 3
Step 1 sequentially adds 12g/L potassium hydroxide into deionized water, 20g/L potassium ferrate, 2g/L titanium sodium fluoride,
10g/L potassium fluoride, 12g/L tertiary sodium phosphate, 15g/L glycerine, the own subunit diamines of 300g/L obtain electrolyte；Electrolyte is existed
30min is sufficiently stirred at room temperature, for use；
Step 2, by AZ31B magnesium alloy (area 5dm2) it is put into 10% (volume fraction) HF, 5% (volume fraction) HNO3
Scavenging period 1min, is then washed in pickling pretreatment liquid；
The AZ31B magnesium alloy handled by step 2 is put into 40g/L sodium carbonate again by step 3,10g/L sodium hydroxide it is clear
In washing lotion, temperature control is 85 DEG C, then scavenging period 4min is washed；
The AZ31B magnesium alloy handled by step 3 is placed in prepared electrolyte by step 4, and AZ31B magnesium alloy connects
Equipment anode is connect, stainless steel carries out micro-arc oxidation treatment to magnesium alloy computor-keyboard after connecting with the mains as cathode.Differential arc oxidation
Electrical parameter are as follows: constant current mode, current density 3A/dm2, frequency 500Hz, duty ratio 15%, positive pulse 1, negative pulse
Number is 0, and the differential arc oxidation time is 20min；
Step 5 will be placed in 70 DEG C of pure water after immersion 4min by the AZ31B magnesium alloy that step 4 is handled, and place into temperature
9min is dried in the baking oven that degree is 100 DEG C.Gained film performance is as shown in table 1.Microscopic appearance is as shown in figure 3, can from Fig. 3
Out, gained film layer has typical " volcano shape " porous structure of differential arc oxidation.Regional area is randomly selected from Fig. 3 carries out power spectrum
As shown in table 1, the essential element in film layer has Mg, Al in matrix as can be seen from Table 1, and comes from solution for analysis
In P, Fe, Ti, wherein Fe, Ti be colour developing element.
Table 1
Embodiment 4
Step 1 sequentially adds 10g/L potassium hydroxide into deionized water, 7g/L potassium ferrate, 3g/L potassium fluotitanate,
12g/L potassium fluoride, 25g/L tertiary sodium phosphate, 20g/L glycerine, 100g/L ethylenediamine obtain electrolyte；By electrolyte in room temperature
Under 30min is sufficiently stirred, for use；
Step 2, by MB8 magnesium alloy (area 1dm2) it is put into 15% (volume fraction) HF, 5% (volume fraction) HNO3Acid
Scavenging period 1min in pretreatment liquid is washed, is then washed；
The MB8 magnesium alloy handled by step 2 is put into 40g/L sodium carbonate, the cleaning of 20g/L sodium hydroxide again by step 3
In liquid, temperature control is 80 DEG C, then scavenging period 4min is washed；
The MB8 magnesium alloy handled by step 3 is placed in prepared electrolyte by step 4, and the connection of MB8 magnesium alloy is set
Standby anode, stainless steel carry out micro-arc oxidation treatment to magnesium alloy computor-keyboard after connecting with the mains as cathode.Differential arc oxidation electricity ginseng
Number are as follows: constant voltage mode, voltage 400V, frequency 500Hz, duty ratio 10%, positive pulse 1, negative pulse number are 1, the differential of the arc
Oxidization time is 10min；
Step 5 will be placed in 70 DEG C of pure water after immersion 3min by the MB8 magnesium alloy that step 4 is handled, and place into temperature
To dry 8min in 110 DEG C of baking ovens.Gained film performance is as shown in table 2.
2 embodiment film performance test result of table
As shown in Table 2, the black film layer that preparation method of the invention obtains is had excellent performance, and film layer L value minimum, can up to 23
96h is tested by neutral salt spray, membranous layer binding force is excellent, and (hundred lattice are tested up to 4B or more), and hemispherical emissivity reaches as high as
0.88, the test of hundred lattice is without film layer obscission after (boiling in 80 DEG C of water) 2h is tested in boiling.
Claims (10)
1. a kind of electrolyte, which is characterized in that the electrolyte composition is as follows:
8~15g/L hydroxide, 10~15g/L fluoride, 20~30g/L phosphate, 4~14g/L ferrate, 1~5g/L
Fluotitanate, 10~20g/L Organic Alcohol, 80~300g/L ablation inhibitor, solvent is deionized water.
2. a kind of electrolyte as described in claim 1, which is characterized in that the electrolyte solute composition is as follows:
10~12g/L hydroxide, 12~14g/L fluoride, 22~25g/L phosphate, 4~14g/L ferrate, 1~5g/
L fluotitanate, 15~18g/L Organic Alcohol, 150~200g/L ablation inhibitor, solvent is deionized water.
3. a kind of electrolyte as described in claim 1, which is characterized in that the hydroxide is sodium hydroxide or hydroxide
Potassium；The ferrate is the mixture of one or both of potassium ferrate, Na2Fe04；Fluotitanate be potassium fluotitanate,
The mixture of one or both of titanium sodium fluoride；Fluoride is one of potassium fluoride, sodium fluoride, hydrogen fluoride ammonia and ammonium fluoride
Or a variety of mixture；Phosphate be sodium dihydrogen phosphate, disodium hydrogen phosphate, tertiary sodium phosphate, calgon, ammonium dihydrogen phosphate,
One of diammonium hydrogen phosphate or a variety of mixtures；Organic Alcohol is one of ethylene glycol, glycerine, isopropanol or a variety of
Mixture；Ablation inhibitor is one of hexa, own subunit diamines, Triaethanolamine or a variety of mixtures.
4. a kind of method for preparing Mg alloy surface black film layer with electrolyte, which is characterized in that specifically includes the following steps:
Step 1 prepares electrolyte, for use；
The electrolyte is electrolyte described in claim 1-3 any one；
Magnesium alloy is first immersed in acid pretreatment liquid and cleans 2~10min, then washed by step 2；
Magnesium alloy after step 2 cleaning is first immersed in alkali cleaning pretreatment liquid and is cleaned, then washed by step 3；
Magnesium alloy after step 3 cleaning is placed in the electrolyte and carries out micro-arc oxidation treatment by step 4, magnesium alloy table
Face forms black film layer；
Step 5, to through step 4, treated that magnesium alloy cleaned, is dried.
5. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that step
Acid pretreatment liquid described in rapid 2 is mixed solution A or mixed solution B, the mixed solution A be hydrofluoric acid, sulfuric acid it is mixed
Solution is closed, the volume fraction of the hydrofluoric acid is 15%~20%, and the volume fraction of the sulfuric acid is 5%~8%；The mixing
Solution B is the mixed solution of hydrofluoric acid and nitric acid, and the volume fraction of the hydrofluoric acid is 5%~10%, the volume of the nitric acid
Score is 5%~10%.
6. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that step
Alkali cleaning pretreatment liquid described in rapid 3 are as follows: concentration is the mixed liquor of 20~40g/L tertiary sodium phosphate and 20~40g/L sodium carbonate, clearly
Washing temperature is 70~95 DEG C, and scavenging period is 2~10min.
7. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that step
Alkali cleaning pretreatment liquid described in rapid 3 are as follows: concentration is the mixed liquor of 20~40g/L sodium carbonate and 10~20g/L sodium hydroxide, clearly
Washing temperature is 70~95 DEG C, and scavenging period is 2~10min.
8. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that step
Alkali cleaning pretreatment liquid described in rapid 3 are as follows: concentration is 40~60g/L sodium hydroxide, and cleaning temperature is 50~70 DEG C, scavenging period
For 1~5min.
9. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that step
Rapid 4 electrical parameters in micro-arc oxidation process are as follows: frequency is 400~800Hz, and duty ratio is 5~30%, positive negative pulse stuffing number ratio 1:0
~10:1, differential arc oxidation time are 5~60min, and powered-on mode is constant current mode or constant voltage mode；
When the powered-on mode is constant current mode, current density is 0.5~60A/dm2；When the powered-on mode is constant voltage mode,
Voltage is 300~580V.
10. a kind of method for preparing Mg alloy surface black film layer with electrolyte as claimed in claim 4, which is characterized in that
Detailed process described in step 5 are as follows: by through step 4 treated magnesium alloy is placed in 60~95 DEG C of pure water cleaning 0.5~
Then 5min puts it into the baking oven that temperature is 80~110 DEG C and dries, drying time is 8~30min.
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| CN112981494A (en) * | 2021-02-08 | 2021-06-18 | 深圳市钧诚精密制造有限公司 | Titanium alloy micro-arc oxidation process with high light absorption rate |
| CN113215635A (en) * | 2021-05-10 | 2021-08-06 | 西安强微电气设备有限公司 | Electrolyte and method for preparing magnesium alloy surface ceramic layer by using electrolyte |
| CN114016108A (en) * | 2021-12-20 | 2022-02-08 | 哈尔滨三泳金属表面技术有限公司 | Surface oxidation film of high-silicon high-copper die-casting aluminum alloy and preparation process thereof |
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